Professional Documents
Culture Documents
Computer Simulated Plant Design For Waste Minimization Pollution Prevention
Computer Simulated Plant Design For Waste Minimization Pollution Prevention
Section 1.15
Section 1.5
Gopal, M. Ramdoss, P., El-Hawagi, M. M., Integrated Design CCT Pollution Prevention, Dec. 19, 1995.
of Reaction and Separation, Systems for Waste Minimiza-
tion. AIChE, Annual Meeting, 1997.
Section 1.16
Section 1.6 Environmental Chemistry Process Laboratory, ecpl.chemistry.
600R94128, A Review of Computer Process Simulation in uch.gr/top.html
Industrial Pollution Prevention, EPA.
Section 1.17
Section 1.7 Dasgupta, S., Lucas, R. E. B., Wheeler, D., Small Plants
OECA, Office of Enforcement & Compliance, EPA Sector Note- Pollution and Poverty:New Evidence from Brazil and
books Profile of the Inorganic Chemical Industry (1995) Mexico, The World Bank Group, a Working Paper, 1998.
EPA/310-R-95-009.
Section 1.18
Section 1.8 Groenendijk, A. J., Plantwide Controllability and Flowsheet
infochem Thermodynamic Models Ther...ransport Properties Structure of Complex Continuous Process Plants, OSPT
Phase Enveloper http://www.infochem.demon.co.uk/ ospt@ct.utwente.nl, 1996.
models.htm#bin
Section 1.19
Section 1.9 Lobor, D. J., J. Organizational Change Mgt., 11(1), 26-37,
Krieger, J. H., Chem. & Eng. News, 3/27/95. http:// 1998, MCB University Press, 0953-4814.
pubs.acs.org/cenear/950327/art08101.html
Section 1.20
Section 1.10 Satoh, Y., Soejima, T., Koga, J., Matsumoto, S., Homma, S.,
Yang, Yihua, Huang, Yinlun, 1988 Annual Tech Program, Sakamoto, M., Takansshi, Nammo, A., Computer Aided
AICHE. Process Flowsheet Design and Analysis System of Nuclear-
Section 2.32
Section 2.20 Rapid Data: Control Kit, Harmonic Software, Inc.
Molecular Phylogenetic Studies, life.anu.edu.au/~weiller/
wmg/wmg.html
Section 2.33
Section 2.21 Radecki, P., (CenCITT), Baker, J., The Clean Process Advisory
Design Synthesis Using Adaptive Search Techniques and Multi- System: Building Pollution Prevention Into Design, CWRT,
Criteria Decision Analyais, www.cs.york.ac.uk/~mark/ CenCITT, NCNS, Envirosense.
mndp/mndp.html
Section 2.34
Section 2.22 Energy Systems Standards/Requirements Identification, http:/
Prof. J. Gasteiger, Research, Computer-Chemie-Centrum, /www.bechteljacobs.com/pqa/compliance/~sproject/
Erlangen. smrfg~16wm.htm
Dr. F. Friedler, Head of the Computer Science Dept., Vesprem,
Hungary.
Section 2.35
es.epa.gov/ncerqa_abstracts/centerscenc...lean/barna.html
Section 2.23
Optimization of Chemical Processes for Waste Minimization Section 2.36
and Pollution Prevention, pprc.pnl.gov/pprc/statefnd/
gulfcoas/optimiz.html
Global Bytes, Chembytes, Chemistry in Britain, Dennis
Rouvray.
Section 2.24
Multisimplex Electronic Newsletter. 12/8/97, webmaster @ Section 3.1
multisimplex.com Minns, D., Zaks, D., Pollution Prevention Using Chemical
http://www.multisimplex.com Process Simulation, NRC-Institute for Chemical Processes
and Environmental Technology Computer Modeling and
Simulation, 1998.
Section 2.25
www.aps.org/meet/CENT99/baps/abs/G7755012.html
Section 3.15
Stowers, M. A., Lesniewski, T. K., Manousiouthakis, V., Pol- Section 3.20
lution Prevention by Reactor Network, AICHE, Annual Friedler, F., Varga, J. B., Fan, L. T., Algorithmic Approach to
Meeting, 1998. the Integration of Total Flowsheet Synthesis and Waste
Minimization, AICHE Symp. Ser., 90(303), 88, 1995.
Varga, J. B., Friedler, L. T., Risk Reduction Through Waste
Section 3.16 Minimizing Process Synthesis, 21st Annual RREL Re-
A General Chemical Kinetics & Sensitivity Analysis Code for search Symposium, Cincinnati, 1995.
Gas-Phase Reactions, Radhakrishnan, K., Bittker, D. L.,
Lewis Research Center, PRCM Poster, http://www.osc.
edu/pcrm/Marek.html Section 3.21
Ianni, J., New Powerful Kinetics Program: KINTECUS (Dec,
Section 3.17 20, 95).
http://www.cpma.u-psud.fr/ccl/244.htm
Kee, R. J., Miller, J. A., Jefferson, T. H., Chemkin-A General
http://www.ioc.ac.ru/chemistry/soft/kintecus.html
Purpose, Problem-Independent, Transportable, Fortran
Chemical Kinetics Code Passage, SAND80-8003. http://www.coma.u-psud.fr/ccl/243.html
Section 4.2
Bumble, S., Emerging Computer Simulation and Control of Section 4.12
Plant Design and Retro-Design of Waste Minimization/ Friedler, F., Fan, L. T., Design of Molecules With Desired
Pollution Prevention in the Late Twentieth and Early Properties by Combinatorial Analysis, 1997, Preprint.
Twenty First Centuries in EPA Region III Waste Minimi-
zation/Pollution Prevention Technical Conference for
Hazardous Waste Generators, Philadelphia, PA, June 3- Section 4.13
5, 1996. Friedler, F., Fan, L. T., Design of Molecules With Desired
Properties by Combinatorial Analysis, 1997, Preprint.
Section 4.3
Section 4.14
Bumble, S., Emerging Computer Simulation and Control of Globus, A., Lawton, J., Wipke, T., Automatic Molecular De-
Plant Design and Retro-Design of Waste Minimization/ sign Using Evolutionary Techniques, draft paper for the
Pollution Prevention in the Late Twentieth and Early Sixth Foresight Conference on Molecular Nanotechnology,
Twenty First Centuries in EPA Region III Waste Minimi- final version submitted for publication in the special
zation/Pollution Prevention Technical Conference for Haz- Conference issue on Nanotechnology. http://science.nas.
ardous Waste Generators, Philadelphia, PA, June 3-5, nasa.gov/globus/home.html
1996.
Section 4.15
Section 4.4
Friedler, F., Varga, J. B., Fan, L. T., Algorithmic Approach to
EDF, Roe, D., Pease, W., Florini, K., Sibergeld, E., Summer, the Integration of Total Flowsheet Synthesis and Waste
1997, www.edf.org., EDF@edf.org Minimization, Pollution Prevention via Process and prod-
uct modifications, AICHE Symposium Series, 90(303),
86.
Section 4.5
Bumble, S., Emerging Computer Simulation and Control of
Plant Design and Retro-Design of Waste Minimization/ Section 4.16
Pollution Prevention in the Late Twentieth and Early Testmart Project to Promote Faster, Cheaper, More Humane
Twenty First Centuries in EPA Region III Waste Minimi- Lab Tests, Academic Environmental Experts Awarded
Section 4.22
Thurston, D., Product and Process Design Tradeoffs for Pol- Section 4.35
lution Prevention, Pacific NW Pollution Prevention Re- Thurston, D. L., Carnahan, J. V., Hazardous Waste, Research
search Center, 1996. and Information Center, 7/31/95.
Section 4.26
Boyd, James, RFF 98-30. Section 5.3
Blurock, E. S., Reaction: Modeling Complex Reaction Mecha-
nisms, Methods of Computer Aided Synthesis, Johannes
Section 4.26 University, Research Institute for Symbolic Computa-
tion, 1995.
NRC’s Institute for Chemical Process and Environmental Tech-
nology (ICPET), Dr. David Minns, www.icpet.nrc.ca/
projects/simu.html Section 5.4
http://www.c-f-c.com/supportdocs/cl2recycle.htm
Section 4.27
Chemical Process Simulation for Waste Reduction, Section 5.5
pprc.pnl.gov/pprc/rpd/fedfund/epa/epastd/chemproc.
html
Hendrikson, J. B., Chem. Tech., Sept.98, (2819), 35-40, ACS,
Teaching Alternative Synthesis. The Syngen Program, in
Section 4.28 Green Chem: Designing Chem. For the Enviromental
FDAT.
SRI’s Consulting Process Economics Program, http://pro-
cess-economics.com
COMPUTER SIMULATED
PLANT DESIGN for WASTE
MINIMIZATION/POLLUTION
PREVENTION
PUBLISHED TITLES
Computer Generated Physical Properties
Stan Bumble
FORTHCOMING TITLES
Computer Modeling and Environmental Management
William C. Miller
COMPUTER SIMULATED
PLANT DESIGN for WASTE
MINIMIZATION/POLLUTION
PREVENTION
Stan Bumble, Ph.D.
LEWIS PUBLISHER S
Boca Raton London New York Washington, D.C.
Library of Congress Cataloging-in-Publication Data
Bumble, Stan.
Computer simulated plant design for waste minimization/pollution prevention / Stan Bumble.
p. cm. -- (Computer modeling for environmental management series)
Includes bibliographical references and index.
ISBN 1-56670-352-2 (alk. paper)
1. Chemical plants--Design and construction--Computer simulation. 2. Chemical
plants--Environmental aspects--Computer simulation. 3. Waste minimization--Computer
simulation. 4. Pollution--Computer simulation. I. Title. II. Series.
TP155.5.B823 2000
660′.28′ 286—dc21 99-057318
This book contains information obtained from authentic and highly regarded sources. Reprinted material is
quoted with permission, and sources are indicated. A wide variety of references are listed. Reasonable efforts
have been made to publish reliable data and information, but the author and the publisher cannot assume
responsibility for the validity of all materials or for the consequences of their use.
Neither this book nor any part may be reproduced or transmitted in any form or by any means, electronic or
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The consent of CRC Press LLC does not extend to copying for general distribution, for promotion, for creating
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Direct all inquiries to CRC Press LLC, 2000 N.W. Corporate Blvd., Boca Raton, Florida 33431.
Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are used
only for identification and explanation, without intent to infringe.
When I asked an EPA repository of information for pollution prevention then occur and a discussion
any references on the subject of this book, I was proceeds on tools for P2.
given a very swift and professional reply: “There isn’t A discussion of the redesign of products and pro-
any.” This was, of course, counter to my experience cesses follows. A very proper set of results for the
of years working on this subject and collecting huge environment, health, and safety in the early design
numbers of papers and referrals that detailed phases of a process is presented. An interesting
progress and enthusiasm for my attempts. A sum- article is summarized that correlates the size of
mary of these findings is in this book. plants and the exposure to pollution. The work on
I think it true that the kind of person who will be the motivation for pollution prevention among top
successful in finding results or creating results in executives in the company is very educational. This
Computer Simulated Plant Design for Waste Minimi- is also true of the article on why the reason for
zation/Pollution Prevention is not the average kind of pollution prevention has not been more favorably
scientist or engineer one finds today. Indeed, the received publicly. A description of a graduate
proper person for this work is a multidisciplined student’s work on a plantwide controllability and
computer scientist, chemical engineer, chemist, flowsheet structure for complex continuous plants
mathematician, etc. There are not many people like is shown. A 3D Design, 3D chemical plant program
that today, particularly creative ones. However, you is described. A computer-aided flowsheet design and
will meet some in this book. analysis for nuclear fuel reprocessing is also de-
The book is divided into five parts and each part scribed.
has a number of sections. The title of the parts Conceptual designs of “clean processes” are shown
describes the main theme of the part but not all of as well as the development of tools to facilitate the
the included matter. design of plants that generate as little pollution as
The first part is entitled Pollution Prevention and possible. Computer Simulated Plant Design for Waste
Waste Minimization. It begins with descriptions of Minimization/Pollution Prevention and flowsheet
process flowsheets and block flow diagrams. It then tools for spreadsheets are shown. Integrated synthe-
describes pollution prevention, cost, and energy. It sis and analysis of chemical process designs using
describes control of exhausts from processes or, in heuristics in the context of pollution prevention are
other words, reduction of emissions. There is then a studied. Also presented are model-based environ-
very brief description of the design or simulation of mental sensitivity analysis for designing a clean
a plant so the reader can get the flavor of it before process plant. Ways to reduce gas emissions in util-
pollution prevention is discussed more thoroughly. ity plants and elsewhere are shown. Upsizing or
Reaction systems and separation systems appropri- inputting the waste of one plant into another is
ate for waste minimization are then introduced. Con- strongly urged. This is further discussed for zero
tinuing in this manner, computer simulation as it emissions where plants are clustered together.
pertains to pollution prevention is introduced. The Permix is a reactor design, from SRI, which helps
Inorganic Chemical Industry Notebook Section from pollution prevention. Batch chromatography is a
EPA is then shown as an example. The important technique that can help develop optimum processes.
introduction to models is introduced next and this is There are P2 opportunities that can be identified
systematized with process models and simulation. from the various sectors mentioned before. Excerpts
Process information and waste minimization are tied on waste minimization are included from the latest
together. The very important cost factors are dis- Federal Register. The definitions of bioaccumulation,
cussed with waste minimization and Department of persistence, and toxicity are discussed as they will
Energy (DOE) processes. A number of sections on be used to spotlight the worst chemical compounds.
Stan Bumble, Ph.D., has guided research, develop- the development of their missile program and with
ment, and engineering at DuPont and Dow Corning the recovery of disaster victims. He has helped (with
with computer programs that optimized the best the assistance of computers) the U.S. Department of
products and properties. He has used computer Justice and the Environmental Protection Agency at
programs for assisting the U.S. government with many hazardous sites such as Love Canal.
Part IV. Computer Programs for the Best Raw Materials and Products of
Clean Processes
4.1 Cramer’s Data and the Birth of Synprops
4.2 Physical Properties form Groups
4.3 Examples of SYNPROPS Optimization and Substitution
4.4 Toxic Ignorance
4.5 Toxic Properties from Groups
4.6 Rapid Responses
4.7 Aerosols Exposed
4.8 The Optimizer Program
4.9 Computer Aided Molecular Design (CAMD): Designing Better Chemical Products
4.10 Reduce Emissions and Operating Costs with Appropriate Glycol Selection
4.11 Texaco Chemical Company Plans to Reduce HAP Emissions Through Early Reduction
Program by Vent Recovery System
4.12 Design of Molecules with Desired Properties by Combinatorial Analysis
4.13 Mathematical Background I
4.14 Automatic Molecular Design Using Evolutionary Techniques
4.15 Algorithmic Generation of Feasible Partitions
4.16 Testsmart Project to Promote Faster, Cheaper, More Humane Lab Tests
4.17 European Cleaner Technology Research
4.18 Cleaner Synthesis
4.19 THERM
4.20 Design Trade-Offs for Pollution Prevention
4.21 Programming Pollution Prevention and Waste Minimization Within a Process
Simulation Program
4.22 Product and Process Design Tradeoffs for Pollution Prevention
4.23 Incorporating Pollution Prevention into U.S. Department of Energy Design Projects
4.24 EPA Programs
4.25 Searching for the Profit in Pollution Prevention: Case Studies in the Corporate
Evaluation of Environmental Opportunities
4.26 Chemical Process Simulation, Design, and Economics
4.27 Pollution Prevention Using Process Simulation
4.28 Process Economics
Conclusions
End Notes
References
List of Figures
Figure 1 Toxicity vs. Log (Reference Concentration)
Figure 2 Parallel Control
Figure 3 Series Control
Figure 4 Feedback Control
Figure 5 A Simple Series Circuit
Figure 6 The Feeding Mechanism
Figure 7 Organisms and Graphs
Figure 8 P-graph of Canaan Geneology Made by Papek Program
Figure 9 Example and Matrix Representation of Petri Net
Figure 10 Petri Nets
Figure 11 Ratio of s in Two Transfer Functions
Figure 12 The Control Kit
Figure 13 The Bode Diagram
Figure 14 Conventional and P-graph Representations of a Reactor and a Distillation Column
Figure 15 Tree for Accelerated Branch-and-Bound Search for Optimal Process Structure
with Integrated in Plant Waste Treatment (Worst Case)
Figure 16 Optimally Synthesized Process Integrating In-Plant Treatment
Figure 17 Conventional and P-Graph Representations of a Separation Process
Figure 18 P-Graph Representation of a Simple Process
Figure 19 Representation of Separator: a) Conventional, b) Graph
It appears as if the successful work to determine ing waste production. Some ideas are also intro-
analytically global solutions for pollution prevention duced that can achieve or help to achieve the results
and waste minimization, while simultaneously en- such as Petri Nets, KBDS, Dependency-Directed
gaged in plant design or simulation, has begun. Backtracking, and the Control Kit for O-Matrix. There
Here we are not concerned with heuristic methods is even a chapter on the construction of new types
but in designs that are necessary and sufficient. of computers.
This requires a new kind of engineer; one that is The third section is called Computer Programs for
very adept in three subjects; chemical engineering, Pollution Prevention and Waste Minimization. This
computer science, and mathematics. It requires yet actually considers computer programs of consider-
another prerequisite: the engineer must be very cre- able assistance to computer simulations and models
ative. of pollution prevention and waste minimization. They
There are not many engineers of this caliber today, include: Process Synthesis (Synphony), Mass Inte-
but it is hoped that with proper training there will be gration, LSENS, Chemkin, Multiobjective Optimiza-
more such engineers in the future. tion, Kintecus, the Simulation Science program, etc.
It is to be emphasized that the mathematics re- Specialized programs such as BDK-Integrated Batch
quired is not the same as that taught today but Development, Super Pro Designer, P2-Edge Soft-
includes “less conventional” subjects or aspects of ware, CWRT Aqueous Stream Pollution Prevention
mathematics, such as discrete mathematics, etc. Design Options Tool, and OLI Environmental Simu-
This book has introduced many topics but has not lation Program (ESP) are also discussed. The con-
gone into each of them very deeply. It was felt more cepts of Green Design and chemicals and materials
important to expose the reader to more of the matter from renewable resources are also examined.
lightly so that his or her preferences would gel. This The fourth section is Computer Programs for the
is true of the first book from this author as well: Best Raw Materials and Products of Clean Processes.
Computer Generated Physical Properties. It shows the invaluable contributions of Cramer’s
The book is divided into five sections. The first is papers to the SYNPROPS method of designing mol-
called Pollution Prevention and Waste Minimization ecules with the most desirable physical and environ-
and it serves as an introduction. It reviews both mental properties available. It also describes Friedler
computer process simulation as well as computer et al.’s method for the design of molecules with
designed pollution prevention and waste minimiza- desired properties by combinatorial analysis. It also
tion. It discusses the meaning and utilization of examines the program THERM for its important
these methods at government agencies, industrial contribution of thermodynamic functions to pro-
corporations, research centers, and countries of the grams of Section three. It discusses the Pinch Tech-
world. It introduces the terminology “Clean Technol- nology, economics, Geographical Information Sys-
ogy.” It examines the effect of such methods on “the tems, health, HAZOP and other features that combine
bottom line.” It examines the effect of upsizing, novel with the computer-assisted simulations.
chemical reactors, OHSA regulations, and risk on The fifth section is called Pathways to Prevention.
the design of clean technology, rather than the de- It has some theoretical considerations for the rest of
sign of “dirty” technology with clean-up at a later the book. Examples include the Grand Partition
time. Function, Cumulants, Generating Functions, the
The second section entitled Mathematical Meth- Path Probability Method, and the Method of Steepest
ods reviews many of the methods available to achieve Descent. It also combines Order and Kinetics to
an optimum using a computer. Such knowledge may obtain the chemical potentials of cancer cells. It also
be necessary to optimize cost, optimize yield, etc., in studies the mechanisms and chemical reactions that
a chemical process while at the same time minimiz- play a part in pollution and pollution prevention.
My thanks to Dr. L. T. Fan for sending me three number of reactors and separators, etc. present. It
items. One is the paper by R. W. H Sargent, “A remains to find the expressions for (A): x, x’, y, y’, u,
Functional Approach to Process Synthesis and its and v and also the values of the exponents (B): g-h,
Application to Distillation Systems”, Computers Chem. h, r, t, s, w, and z. This is done by the methods of
Eng., 22(1-2), 31-45, 1998. In it he shows that Bumble and Honig and Hijmans and DeBoer for (A)
Douglas’s hierarchical approach to process design, by setting up 3 sets of equations: Equilibrium Equa-
with successive refinement of models as required to tions, Consistency Equations, and Normalizing Equa-
resolve choices, can be embedded in a rigorous im- tions from Statistical Mechanics. The valisues for the
plicit enumeration procedure for finding the optimal set B is then found by inserting the problem into
design, within the accuracy implied by the final SYPROPS and using the Optimization routine for Q
model. This is an advantage because the final design with proper constraints. When done there will be an
is verified by use of models as detailed and accurate optimized chemical flowsheet.
as desired, while limiting computational effort by Another way to proceed involves the Path Integral
use of simpler models during development of the
design. He also uses the representation of a process M = ∫ba exp(i/h) S[b,a] Dx(t)
as a state-task network which contains a connected
path from each feedstock to some product and con- and the entropy can be given analytically
versely from each product to at least one feed; more-
over each intermediate state and task must be on at S{pis(n)}=-N∑m=an yn(m)∑isLis(m)pis(m)lnpis(m)
least one such path. We can then devise an algo-
rithm which generates all feasible state-task-net- Also other techniques viewed were the random
works. These can then be evaluated with an implicit walk method, order -disorder methods, and the
enumeration procedure, at the same time refining Wiener method.
models as required to resolve the choices. Consider a flexible chain of fixed length constrained
Dr. Fan also sent me the latest flowsheet for the to lie on a square lattice. If one end is fixed at the
structure of SYNPHONY. It is shown as Figure 83. origin, how many configurations of the chain will
He also brought to my attention the article “Unique give the other end x coordinate c?
Features of the Method for Process Synthesis Devel- At each point n the chain may follow any of 4
oped by F. Friedler, L.T. Fan, and Associates”, which paths. If it follows plus or minus y it contributes no
was discussed earlier. new value to the x coordinate. However, plus or
Figure 61 shows paths followed in going from one minus x paths will contribute plus or minus 1 to the
occupied rhombus figure to another. It turns out x coordinate, so the generating function is
that a direct product expression
____________
Q = (x)g-h(x’)h(y)r(z)t(y’)s.
G(L, x)=(1/z+2+z)L =(1+2z+z2)L/zL =(1+z)2L/zL
Here x and x’ are different sites on a geometrical
figure and y, y’, and z are interactions between By the binomial theorem the coefficients can be
different bodies on these sites. The exponents g-h, h, seen to be
r, t, and s are the counts of the number of such sites
and interactions that there are. Now I will multiply (2L)!/(L-D)!(L+D) where D = pL
the above equation by (u)w(v)t. Here u and v are the
reactor and the separator, etc. W and t are the Then g(L,x) = (2L)!/((1-p)L)!((1-p)L)!
H
ar
an
Nah
or
Abram
Abram
ah
Lot
lk
Mi
Be Lo
the t
r Lo da 1
Sa t da 2
ral
ka
La
Isa be
Re
ba
ac
n
Jaco Ra
b
l
ch Leah
ae
Jacob
Ja Jaco
m
co b ea
Ish
au b l
Es
au
Es
u
Esa
Mahatha
in
eon
Naphtall
Asher
Ruben
Benjam
ph
n
Sim
Da
Jose
FIGURE 8 P-graph of Canaan geneology made by Papek
FIGURE 7 Organisms and graphs. program.
FIGURE 9 Example and matrix representation of Petri net. FIGURE 10 Petri nets.
9.8985(s + 1) + 1
2
2
H (s) =
2
s s
s + 1
s
+ 0.6607 + 1
s
+1
0.3 2.119 2.119 15
9.8985(0.5s 2 + 1.5s + 1)
=
s(0.0496s + 0.8265s3 + 1.5051s 2 + 3.7118s + 1)
4
FIGURE 17 Conventional and P-graph representations of a FIGURE 18 P-graph representation of a simple process.
separation process.
FIGURE 23 P-Graph where A, B, C, D, E, and F are the FIGURE 24 P-graph representation of a process structure
materials and 1, 2, and 3 are the operating units. involving sharp separation of mixture ABC into its three
components.
FIGURE 26 Enumeration tree for the basic branch and FIGURE 27 Enumeration tree for the accelerated branch
bound algorithm which generates 9991 subproblems in the and bound algorithm with rule a(1) which generates 10 sub-
worst case. problems in the worst case.
1 2 3 4
1 2 3 4
5 6 7 8
5 6 27 7 8
9 10 11 9 10 11 12 13
16 18 14 15 16 17 18 19 20
SW SW HCI H2SO4
21 22 21 22 23
ww ww
24 24 25 26
PMM PMM SW SW
FIGURE 34 Maximal structure of the PMM production pro- FIGURE 35 Maximal structure of the PMM production pro-
cess without integrated in-plant waste treatment. cess with integrated in-plant waste treatment.
N OR OR
O O
CO2R CO2R
Silylester (1) Hydroxyester (2)
R H H
O N
O
CO2R
Lactone (3)
• SYNGEN is a unique program for automatic generation of the shortest, most economic organic synthesis
routes for a given target compound.
• SYNGEN is based on Professor Hendrickson’s Half-Reaction Theory. It does not require a reaction
database.
• SYNGEN is easy to use. After input of a target structure, the program automatically generates all the
shortest routes. Then, if you press
Step button, synthesis routes are ordered by reaction steps, with the shortest one first.
or simply type in
If you press
Cost button, synthesis routes are ordered by overall cost, witht the cheapest one first.
If you want to see those routes belonging to bond set 4, for example, you just need to type in 4 in the
Bondset: space.
FIGURE 50 SYNGEN.
Z
O
Z
O
Z
O N
A1 - 2F
O
Z
Z
O N N+
O HN
A3 - 31
P1 - 2F
Z Z
O O
O R1 - 12 O
N+ N
X HN
HN
ArSO2CN
∆/MeOTf N+ N
O O
(2)
SO2Ar
(2)
COOR
N
COOR
N R
FIGURE 52 Any carbon in a structure can have four general kinds of bonds.
O O RO
RO RO
O
+
E E
O O O
O O
O O
SOCF3 SO2CF3
Pft
O Pft
S OcN
NC O S
O
+ NC O
OcN TFAA
OH
X
X
FIGURE 54 Pericyclic reaction to join simple starting materials for quick assembly of morphinan skeleton.
O O O
CO2 F1.2E
EO O
O O
P1.2F
E1.2E A1.12 P3.31 B2.12
O O
O O CO2
O O
FIGURE 55 Sample SYNGEN output screen from another Figure 56 Second sample SYNGEN output screen.
bondset.
FIGURE 59 Effect of considering larger basic figures. FIGURE 60 The rhombus approximation.
FIGURE 77 Trade-off between capital and operating cost for a distillation column.
FIGURE 79 Acetone-Formamide and chloroform-methanol FIGURE 81 McCabe-Thiele for (a) minimum stages and (b)
equilibrium diagrams showing non-ideal behavior. minimum reflux.
FIGURE 83 P-Graph of the process manufacturing required FIGURE 84 Enumeration tree for the conventional branch-
product H and also yielding potential product G and dispos- and-bound algorithm.
able material D from raw materials A, B, and C.
1.1 Chemical Process Structures Though the first computer calculations to process
design were limited to design calculations involving
and Information Flow a single unit such as a heat exchanger or a flash
Systematic study of structural problems is of rela- separator, it did not take very long before chemical
tively recent origin in chemical engineering. One of engineers recognized the far greater potential of a
the first areas to receive such attention is process process flowsheet simulator. In the years since the
flowsheet calculations. These calculations typically first such program was reported, process flowsheeting
occur in process design. programs have become the accepted workhorse of
Process design may be perceived as a series of many a process design organization. One feature of
distinct tasks. Starting with a market need or a such a program is its capability to input and modify
business opportunity, a number of process alterna- the process flowsheet configuration and to perform
tives are created or synthesized. The task of creating design calculations involving a process flowsheet.
these alternatives is sometimes referred to as pro- Because of the need to enhance material and energy
cess synthesis. The outcome of process synthesis is utilization, a chemical process is typically highly
usually expressed in terms of process flowsheets. integrated. Unconverted reactants and unwanted
The best solution is arrived at by systematically byproducts arising from incomplete chemical con-
evaluating each of these alternatives. This quantita- version are typically recycled after they are first
tive evaluation usually begins with the material and separated from the desired products. The recycle
energy balances, followed by equipment size and enhances the overall chemical conversion and yield.
costing and culminates in an analysis of the eco- Also, the reaction or separation may have to be
nomic merits of the process. As the initial choice of carried out at a high temperature. In order to mini-
the process is not expected to be optimal, it is usu- mize energy requirements, a feed-effluent heat ex-
ally possible to improve the process by a different changer may be introduced to recover waste heat
choice of process flows and conditions. This is called and to preheat the feed. The ideal design structure
parameter optimization. Some of these decided vari- of a process flowsheet is a tree from the viewpoint of
ables may be continuous, others may be discrete design calculations. Then the calculations can pro-
such as stages or size of equipment. ceed sequentially. This is never ideal from the view-
A process can be improved by a different choice of point of material and energy utilization. The intro-
processing units and interconnections. The task of duction of recycle streams and heat exchangers
identifying such improvements is termed structural creates more cyclic structures in a process flowsheet
optimization. While some structural improvements and makes it more difficult to determine an appro-
are but minor modifications of the same process, priate calculation sequence.
others give rise to different processes.
The above description is of course a gross simpli- 1.2 Analysis Synthesis & Design of
fication of the reality. In practice, these tasks are not
always neatly partitioned, nor are they carried out in
Chemical Processes
sequence, nor to completion. This evaluation or op- Three principal diagrams for a chemical process are
timization may be truncated once the outcome is the block flow diagram (BFD), process flow diagram
apparent, or its purpose is fulfilled. However, it is an (PFD) and the piping & instrumentation diagram,
iterative nature of process design activities and the (P&ID). Design is an evolutionary process which can
central role of process flowsheet calculations and be represented by the sequence of process diagrams
the heart of process evaluation and optimization. describing it. To begin, an input-output diagram
Because the calculations are so repetitive, efficiency, may be sketched out. One can then break down the
reliability, and accuracy of the solution procedure process into its basic functional elements such as
deserve special attention.
November 16, 1994, the United States Environmen- EPA would implement several mechanisms within
tal Protection Agency released a report entitled “The the RCRA REGULATORY framework including:
Waste Minimization National Plan”. This plan estab-
lishes three goals. 1. Developing a program for working with genera-
tors to promote waste minimization.
1. To reduce, as a nation, the presence of the most 2. Issuing revised guidance on the use of Supple-
persistent, bioaccumulative, and toxic constitu- mental Environmental Projects (SEPs).
ents by 25% by the year 2000 and by 50% by 3. Working with EPA Regions and states to provide
the year 2005. waste minimization training for inspectors, per-
2. To avoid transferring these constituents across mit writers, and enforcement officials.
environmental media. There are also a number of Institutional Mecha-
3. To ensure that these constituents are reduced nisms that are not cited here. However, the report
at their source whenever possible, or, when not ends with the statement that EPA will publish guid-
possible, that they are recycled in an environ- ance to regions, states, and industry, identifying
mentally sound manner. when and how waste minimization information
should be made available to the public during the
1.33 Federal Register/Vol. 62, No. permit process.
120/Monday, June 23, 1997/
Notices/33868 1.34 EPA Environmental Fact
This plan presented a combination of five objectives
Sheet, EPA Releases RCRA Waste
of voluntary, regulatory, and institutional mecha- Minimization PBT Chemical List
nisms to achieve these objectives. They were: States, industry environmental groups, and citizens
advised EPA in 1994 that waste minimization should
1. Develop a framework for setting national priori- consist of the following:
ties; develop a flexible screening tool for identi-
fying priorities at individual facilities; identify Reduce as a nation the presence of the most persis-
constituents of concern. tent, bioaccumulative, and toxic chemicals in
2. Promote multimedia environmental benefits and industrial hazardous wastes by 25 percent by
prevent cross-media transfers. the year 2000 and by 50 percent by the year
3. Demonstrate a strong preference for source re- 2005.
duction; shift attention to the nation’s hazard- Avoid transferring these chemicals across environ-
ous waste generators to reduce hazardous waste mental media.
generation at its source. Ensure that these chemicals are reduced at their
4. Clearly define and track progress; promote ac- source whenever possible, or, when not pos-
countability for EPA, states, and industry. sible, that they are recycled in an environmen-
5. Involve citizens in waste minimization imple- tally sound manner.
mentation decisions.
To address these recommendations, EPA first de-
EPA promised to help in such ways as using the veloped the Waste Minimization Prioritization Tool,
results from the prototype screening approach to set which scores thousands of chemicals based on their
An analog formulation, in its most simple form, is LC50/100 = p’/k(1 - exp - (kmt)) = p’/k(f(t)). (2)
used to express toxicity for six mammals and eight
chemical species. General control theory is discussed In practice, when t is very large, the function of t, (1-
and the system transfer function is shown to be exp(k/mt)), is equivalent to unity and an additive
similar to the analogue toxicity equation. Also gen- constant, C, is added so that
eral kinetic equations of Lotka are of this nature.
Electrical network equations can be solved for LC50/ LC50/100 = p’/k + C. (3)
100 for man and animals in a more complex system
by the network systems model of the environment. Then each animal has a different physiological fac-
By analogy then, the system can be controlled by tor p’, each chemical has a different value of k, and
feedback control or any of a dozen methods to re- when LC50/100 = y is plotted vs. 1/k = x, then the
duce the overall LC50/100 of the ecological popula- experimental data fall on a straight line with slope p’
tion, at any site, by reducing the emissions of spe- and intercept C (Figure 1). The eight chemicals used
cific chemicals to a site whose ecological nature is to plot Figure 1 were vinyl chloride, xylene, acrolein,
known. formaldehyde, benzene, styrene, epichlorohydrin, and
chlorobenzene. The data was extended to the horse
Introduction with data from the University of Pennsylvania Vet-
While studying risk and toxicology of small mam- erinary School and found to fit logically on the simple
mals for the ecological impact on various Superfund graphs.
sites, it was discovered that the use of simple ana- The more rigorous derivation leads to an expres-
logue techniques led to an acceptable description of sion with hyperbolic trigonometric functions as well
g(s) = Q(s)/P(s) = a0+a1s + as2 + — + where k1 is the rate equation in the forward reaction
A1/(s – s1) + — +a2/(s – s2) + and k–1 is that in the reverse directgion. This regu-
Ap2/(s – sp2)2 + —Apr/(s – spr)r. (8) lation endows biological systems with the possibility
to choose between two or more well distinct states of
The inverse transform is then regime. This, characterized by multiple steady states,
is epigenetic. It is ensured by feedback loops.
g(t) = a0u1(t) + a1u2(t) + a2u3(t) + — + A1exp(s1t) +
A2exp(s2t) + — + Apr/(r-1)!tr-1exp(spt)(–1)r–1 (9) Networks and Ecosystems
In [14], Lotka proposes general kinetic equations
where u is the unit step function. In this connection, that lead to similar results (17) as (9) or (9a). If X is
it is noted in a text on ecotoxicity that a function mass, and excess xi of each mass X over correspond-
such as ing equilibrium values is
xn = Gn1exp(m1t) + Gn2exp(m2t) + —
Gnnexp(mnt) + Gn11exp(2m1t) + — Consider LdA/dt + RA = 1 (24)
If some of G are positive and some are negative, Solution of the equation,
then oscillations may occur. If the roots m are com-
plex, exp (a + ib)t = exp(at)(cosbt + isinbt), and there LdI/dt+RI = E0sinwt (28)
are damped oscillations about equilibrium.
Consider a general type of network [15] made up would also lead to (27( for I(o) = 0)). (Figure 5 shows
of m independent circuits. Each circuit contains an a simple series circuit).
e.m.f., resistances, inductances and capacitances, It is now seen that if we designate R = k, L = m, E
then each circuit current will flow. Letting zjk(p) be = p’, etc., by analogy, we can solve (18) and (21) for
the operator acting on Ik in the jth equation an ecological or anthropomorphic system and we
will obtain LC50/100 for man and other mammals
zjk = Ljkp + Rjk + 1/(Cjkp), then (19)
Quadratic programming problems are more complex 2.6 Elements of Graph Theory
than LP problems, but simpler than general NLP
problems. Such problems have one feasible region Graphs have proven to be an extremely useful tool
with “flat faces” on its surface, but the optimal for analyzing situations involving a set of elements
solution may be found anywhere within the region in which various pairs of elements are related by
or on its surface. Large QP problems are subject to some property. Most obvious are sets with physical
many of the same considerations as large LP prob- links, such as electrical networks, where electrical
3.1 Pollution Prevention Using recycling such batteries using pyrometallurgical dis-
tillation.
Chemical Process Simulation Three goals for green design are:
Chemical process simulation techniques are being
investigated as tools for providing process design Reduce or minimize the use of non-renewable
and developing clean technology for pollution pre- resources;
vention and waste reduction.
HYSYS, commercially available process simula- Manage renewable resources to ensure
tion software, is used as the basic design tool. ICPET sustainability and;
is developing customized software, particularly for
reactor design, as well as custom databases for the Reduce, with the ultimate goal of eliminating
physical and chemical properties of pollutants, that toxic and otherwise toxic harmful emissions to
can be integrated with HYSYS. Using these capabili- the environment, including emissions contrib-
ties, studies are being carried out to verify reported uting to global warming.
emissions of toxic chemicals under “voluntary-ac-
tion” initiatives and to compare the performance of The object of green design is to pursue these goals
novel technology for treating municipal solid waste in the most cost-effective fashion. A green product
with commercially available technology based on or process is not defined in any absolute sense, but
incineration processes. only in comparison with other alternatives of similar
function. For example, a product could be entirely
3.2 Introduction to the Green made of renewable materials, use renewable energy,
and decay completely at the end of its life. However,
Design this product would not be green if, for example, a
“Green Design” is intended to develop more environ- substitute product uses fewer resources during pro-
mentally benign products and processes. Some ex- duction and uses or results in the release of fewer
amples of practices include: hazardous materials.
Solvent substitution in which single use of a toxic Green products imply more efficient resource use,
solvent is replaced with a more benign alternative, reduced emission, and reduced waste, lowering the
such as biodegradable solvents or non-toxic sol- social cost of pollution control and environmental
vents. Water based solvents are preferable to organic protection. Greener products promise greater profits
based solvents. Technology change such as more to companies by reducing costs (reduced material
energy efficient semiconductors or motor vehicle requirements, reduced disposal fees, and reduced
engines. For example, the Energy Star program speci- environmental cleanup fees) and raising revenues
fies maximum energy consumption standards for through greater sales and exports.
computers, printers, and other electronic devices. How can an analyst compare a pound of mercury
Products in compliance can be labeled with the dumped into the environment with a pound of di-
“Energy Star.” Similarly, “Green Lights” is a program oxin? Green indices or ranking systems attempt to
that seeks more light from less electricity. summarize various environmental impacts into a
Recycling of toxic wastes can avoid dissipation of simple scale. The designer or decision maker can
the materials into the environment and avoid new then compare the green score of alternatives (mate-
production. For example, rechargeable nickel-cad- rials, processes, etc.) and choose the one with mini-
mium batteries can be recycled to recover both cad- mal environmental impacts. This would contribute
mium and nickel for other uses. Inmetco Corpora- to products with reduced environmental impacts.
tion in Pennsylvania and West Germany are routinely
Free radicals are important intermediates in natural Provide more effective solutions to complex en-
processes involved in cytotoxicity, control of vascu- vironmental problems by developing the capa-
lar, tone, neurotransmission. The chemical kinetics bility to perform multipollutant and multimedia
of free-radical reactions control the importance of pollutant assessments.
competing pathways. Equilibria involving protons
often influence the reaction kinetics of free radicals Provide a computational and decision support
important in biology. Free radicals are very impor- environment that is easy to use and responsive
tant in atmospheric chemistry and mechanisms. to environmental problem solving needs to key
Yet, little is known about their physical or biological federal, state and industrial policy-making or-
properties. ganizations.
In 1958, White, Johnson, and Dantzig (at Rand)
published an article entitled “Chemical Equilibrium Thus, EPA participates in the NREN, ASTA, IITA,
in Complex Mixtures.” It was a method that calcu- and BRHR components of the HPCC Program, where:
lated chemical equilibrium by the method of the NREN: increasing access to a heterogeneous com-
minimization of free energy. It was an optimization puting environment, ASTA: environmental assess-
problem in non-linear programming and was used ment grand challenges, IITA: enhancing user access
in industry and in defense work on main frame to environmental data and systems, BRHR: broad-
computers. PCs were not available at that time. Also, ening the user community tools by adapting them to
environmental matters were not as much of a con- a distributed heterogeneous computing environment
cern as they are now. that includes scalable massively parallel architec-
The literature and computer sites on Geographic tures.
Information Sytems (GIS) are rife with a tremendous Environmental modeling of the atmosphere is most
amount of information. The number of such maps frequently performed on supercomputers. UAM-
are increasing greatly every day as exploration, as- GUIDES is an interface to the Urban Airshed Model
sessment, and remediation proceeds across the world (UAM). An ozone-compliance simulator is required
wherever environmental work is taking place. by the Clean Air Act of 1990, so that modeling
There are many software programs for geotechnical groups across the United States have asked the
and geo-environmental and environmental model- North Carolina Supercomputing Center (NCSC) to
ing. They are in the category of contaminant model- develop a portable version. NCSC’s Environmental
ing. Most of them are in the DOS platform and are Programs Group used the CRAY Y-MP system, a
public domain. previous-generation parallel vector system from Cray
Massively parallel computing systems provide an Research to develop UAMGUIDES as a labor-saving
avenue for overcoming the computational require- interface to UAM. Running UAM is very complex.
ments in the study of atmospheric chemical dynam- The Cray supercomputers have, since then, been
ics. The central challenge in developing a parallel air upgraded. Computational requirements for model-
pollution model is implementing the chemistry and ing air quality have increased significantly as mod-
transport operators used to solve the atmospheric els have incorporated increased functionality, cov-
reaction-diffusion equation. The chemistry operator ered multi-day effects and changed from urban scale
is generally the most computationally intensive step to regional scale. In addition, the complexity has
in atmospheric air quality models. The transport grown to accommodate increases in the number of
operator (advection equation) is the most challeng- chemical species and chemical reactions, the effects
ing to solve numerically. Both of these have been of chemical particle emissions on air quality, the
improved in the work of Dabdub and Seinfeld at Cal. effect of physical phenomena, and to extend the
Tech. and have been improved in the next genera- geographical region covered by the models.
4.1 Cramer’s Data and the Birth of 4.2 Physical Properties form
Synprops Groups
Cramer’s data (Figures 43 and 44) is in the table of It has also been known that a wide range of proper-
group properties. Results so obtained were from ties can be derived using The Principle of Corre-
extensive regressions on experimental data from sponding States which used polynomial equations
handbooks and were tested and statistically ana- in reduced temperature and pressure. In order to
lyzed. The data was used to predict physical proper- obtain the critical properties needed for the reduced
ties for other compounds than those used to derive temperature and reduced pressure, the critical con-
the data. In this work, optimization procedures are stants are derived from the parameters for the groups
combined with the Cramer data (in an extended of which the molecules are composed.
spreadsheet), and applied for Pollution Prevention Thus, the treatment of many molecules through
and Process Optimization. In addition, Risk Based their composite groups and the connection with their
Concentration Tables from Smith, etc., are included properties becomes an exercise of obtaining good
as constraints to ensure that the resulting compos- data to work with. This is particularly difficult for
ite structures are environmentally benign. drug and ecological properties that are not in the
During the course of many years, scientists have public domain.
recognized the relationship between chemical struc- Cramer’s method consisted of applying regressions
ture and activity. Pioneering work has been done by to data from handbooks, such as the Handbook of
Hammett in the 1930s, Taft in the 1950s, and Hansch Chemistry and Physics, etc., to fit the physical prop-
in the 1960s. Brown also recognized the relation erties of molecules with the groups comprising their
between steric effects and both properties and reac- structures. The results considered about 35 groups
tions. QSAR methodologies were developed and used and were used in the Linear-Constitutive Model and
in the areas of drug, pesticide, and herbicide re- a similar number of groups (but of a different na-
search. In the 1970s, spurred by the increasing ture) were used in the Hierarchical Additive-Consti-
number of chemicals being released to the environ- tutive Model. Statistically a good fit was found and
ment, QSAR methods began to be applied to envi- the prediction capabilities for new compounds were
ronmental technology. found to be excellent.
Meanwhile, the hardware and software for per- Twenty-one physical properties were fitted to the
sonal computers have been developing very rapidly. structures. The Properties (together with their di-
Thus the treatment of many molecules through their mensions) were Log activity coefficient and Log par-
composite groups and the connection with their tition coefficient (both dimensionless), Molar refrac-
properties becomes an exercise of obtaining good tivity (cm3/mol), Boiling point (degrees C.), Molar
data to work with. A Compaq 486 Presario PC with volume (cm3/mol), Heat of vaporization (kcal./mol),
a Quattro Pro (version 5.0) program was available. In Magnetic susceptibility (cgs molar), Critical tempera-
the “Tools” part of the program is an Optimizer ture (degrees C.), Van der Waals A1/2 (L atm1/2/mol),
program, which was used in this work. The technol- Van der Waals B (L/mol), Log dielectric constant
ogy of the modern PC was matched with the power (dimensionless), Solubility parameter (cal/cm3), Criti-
of mathematics to obtain the following results. The cal pressure (atm.), Surface Tension (dynes/cm),
values of the parameters B, C, D, E, and F for thirty- Thermal Conductivity (104 × (cals-1cm-2(cal/cm)-1),
six compounds are shown in Figure 41 and used to Log viscosity (dimensionless), Isothermal (m2/mol ×
obtain physical properties and Risk Based Concen- 1010), Dipole moment (Debye units), Melting point
trations. (degrees C), and Molecular weight (g./mol). Later the
5.1 The Grand Partition Function Suppose further that r short range bonds and t long
range bonds are formed. The equilibrium constant
Upon studying such topics as mass integration of for such a “reaction” will then be
El-Hawagi et alia, certain matters seem to occur in
the mind of a theoretical physicist. First of all, the mis = [x]g-h [x’]h [y]r [z]t [y’]s
difference between energy integration and energy
plus mass integration seem similar to that between and it remains to find the values of x, x’, y, and z.
the canonical ensembles and the grand canonical This can be done by setting up the various sets of
ensembles of statistical mechanics in the minds of equations among the various geometrical figures
the theoretical chemist and physicist. Very briefly, involved. Such equations are called consistency equa-
the Grand Canonical Ensemble (G.P.F.) is defined as tions and normalizing equations.